Cyclic ketonic compound and process of making it



Patents Feb. 12, i929.

tnaooz INRICE GREENE, 0F HOOHST-ON-THE-MAHT, GERMANYK'ASSIGNDR TO GBASSELLI DYESTUFI CORPORATION, OE NEW YORK, I l". Y., A CORPORATION 013 DELAWARE.

OYGLIC KETONIG COMPOUND AND P3001255 0F MAJKDIG Id.

We same. a utation filed June re, 1927, serial no. teams,

The present invention relates to new cyclic ketonic compounds and to a process of preparing the same. i

l have found that by causing maleic anhydride to act upon an aromatic hydrocarbon having an unsubstituted eri-position as represented by the general formula:

in which Xstands for hydrogen or a monovalent substituent and the two i s stand for hydrogen or jointly for the group in the presence of an acid condensing a ent new condensation. products are obtained fill showing the characteristics of cyclic hetones.

in the course of the reaction, which obviously occurs in two stages, there is probably at first formed a carboxylic acid with an open chain changing into the rin hetone during the further condensation. fiius when operating for instance in presence of a low-boiling solvent such as carbon disulfide, generally at temperatures up to the boiling point of-carbon disulfide, only the carboxylic acidis obtained which can be easily transformed into the corresponding ring hetone by further condensing it at a raised temperature, for instance with molten sodium-aluminium chloride. it is, of course, also possible to produce the ring ketone by a single operation, for instance byfusing the hydrocarbon in question with maleic anhydride in presence of sodiumaluminium chloride.

Whereas the carboxylic acids usually dissolve in strong sulfuric acidto a yellowishred to blood-red solution and without any fluorescence, the solutions of the ring lretones in sulfuric acid, which for the most part are of a faintly yellow coloration, show a pronounced moss-green fluorescence. 1

The saidnew ring ketones are valuable intermediate products and are intended to be used as starting materials in the production of dyestufis.

and in Germany Juuebt, 118%.

The following examples illustrate my inpoured into 2000 parts of water, the nitrobenzone is distilled 0d by means of water vapor and the resulting condensation product is filtered by suction. In order to puri the same, it is dissolved in dilute sodium car onate, the solution is filtered and the product is reprecipitated from the filtrate by means of dilute hydrochloric acid. it constitutes a yellow carboxylic acid dissolving in concentrated sulfuric acid to an orange-red solution. When recrystallized from benzene, it melts at 139 C. to 140 0.

The said carboxylic acid can be fused with sodium-aluminium chloride to form the corresponding ring hetone by heating 15 parts of the acid with 100 parts of sodium-aluminimum chloride to about 120 C. to 140 C. until the formation of the ring hetone is complete. For worg up the product, the melt is decomposed with much water, the mass is filtered by suction and the residue washed first with hot dilute hydrochloric acid and then with water. in order to purify the res idue, it is dissolved in sodium carbonate, the

mass is filtered, the finishedring ketone, is

the evolution of hydro- I of colorless leaflets melting at 186 C. to 18 7 Q. it dissolves in stron sulfuric acid to a faintly yellow solution with an intense mossgreen fluorescence.

(2) Into 480 parts of molten sodium-alu-- minium chloride is introduced by portions at a temperature of about C. to C. a powdered mixture of 26 parts of naphthalene and 22 parts of maleic anhydride, and the molten mass is maintained at this temperature until the condensation to the rin ketone is complete. The ring ketone which 1s immediately formed when operating as above indicated, is worked up and purified in the manner described in Example (1). lized from dilute alcohol, it melts at 186 C. to 187 C. It is identical with the cyclic ketocarboxylic acid obtainable according to Example p (3) Into a solution, heated to boiling, of 30,8 parts of acenaphthene and 22 parts of maleic anhydride in 150 parts of carbon disulfide are introduced by and by 30 parts of aluminium chloride, and after the whole of the aluminium chloride has been added, the mass is further heated to boiling in a reflux apparatus for about 3 hours. The condensation product'formed is worked up and purified as indicated in Example (1). A carboxylic acid is finally obtained, having obviously an open chain; recrystallized from dilute alcohol it forms yellowish leaflets, melting at 154 C. to 155 C. and dissolving in concentrated sulfuric acid to a blood-red solution.

its quantity of sodium-aluminium chloride under the conditions stated in Example (1) of almost colorless needles, melting at 216 C.

I beta-naphthol or t to 217 C. and dissolving in concentrated. sulfuric acid to a; tense moss-green ellow solution with an inuorescence. lit is'identical with the ring ketocarboxylic acid obtainable according to Example (4).

(4) Into 200 parts of molten sodium-aluminium chloride is introduced by portions at about 120 C. to 130 U. a powdered mixture of 154 parts of acenaphthene and 110 parts of maleic anhydride, and the molten mass is maintained at the tem erature until the formation of the ring etone is complete. The condensation product can be worked and purified as indicated in Exam le Thus a ring ketocarboxylicacid is o tained, which when crystallized from dilute alcohol forms almost colorless" needles,

an intense moss-green fluorescence.

In the same manner as naphthalene an acenaphthene themselves, also thereof having a free peri-position, as for instance l-methylnaplhthale'ne or alpha and e like, can be converted ring ketones by the into the corresponding action of maleic anhydride with the aidof aluminium chloride or ferric chloride. hydrocarbons and the derivatives thereof Other having a free pen position, as for instance anthracene, behave 1n exactly the same manner.

In the following claims the term aromatic having an; unsubstituted peiihydrocarbons Recrystal- By melting this acid with about seven times melting at 216 C. to 217 C. and dissolving in concen-' trated sulfuric acid to a yellow solution with: f

.derivatives moaooa position is understood to comprise also dc.- rivatives or substitution'pr'oducts thereof.

I claim:

1. The process which comprises causing maleic anhydride to act upon an aromatic hydrocarbon having an unsubstituted periposition in the presence of an acid condensing agent and a solvent at a temperature up to the boiling point of carbon disulfide.

2. The process which comprises causing maleic anhydride to act upon an aromatic hydrocarbon havingan unsubstituted penposition inthe presence of aluminum chloride and a solvent at a temperature up to the boiling point of carbon disulfide.

3. The process which comprises heating to boiling a mixture of maleic anhydride', an aromatic hydrocarbon having an unsubstituted peri-position and carbon disulfide in the presence of aluminum chloride.

4. The process which'comprises causing maleic anhydride to act upon an aromatic hydrocarbon having an unsubstituted periposition in the presence of an aci condensing agent and a solvent at a temperature up to the boiling point of carbon disulfide and itusing the intermediate product thus obtainable with sodium aluminum chloride.

5. The process which comprises causing maleic anhydride to act upon an aromatic hydrocarbon having an unsubstituted periposition in the presenc of aluminum chlorideand a solvent at a tgimperature u to the boiling point of carbon isulfide, an the intermediate product thus obtainable with sodium aluminum chloride.

- 6. The process which comprises heating to boiling a mixture of maleic anhydride, an aromatic hydrocarbon having an unsubstituted eri-position and carbon disulfide in the presence of aluminum chloride and fusing the intermediate product thus obtainable fusing Y with sodium aluminum chloride at a temperature of about 120 tor140 G.

maleic anhydride tof'act upon a compound of the general iornnula'iki 1 Y a n wherein X stands forhy'drogenor a monovalent substituent and the two. Ys stand for hydrogen atoms or jointly for the group inthe'presence ofan acid condensin 'a entand a solvent at a temperature up tot 'e 01ling point of carbon disulfide, and fusing the intermediate product thus obtainable with sodium aluminum chloride.

8. The process which comprises causing maleic anhydride to act upon'a compound of the general formula:

wherein X stands for hydrogen or a monovalent substituent and the two Ys stand for hydrogen atoms or jointly for the group (Bi -10H, l

in the presence of aluminum chloride and a solvent at a temperature up to the boiling point of carbon disulfide and fusing the intermediate product thus obtainable with sodium aluminum chloride.

9. The process which comprises heating to boiling a mixture of maleic anhydride, a compound of the general formula:

wherein X stands for hydrogen or a monovalent substituent and the two Ys stand for hydrogen atoms or jointly for the group vent at a temperature u to the-boiling point of carbon disulfide, an fusing the intermediate product thus obtainable with sodium aluminum chloride.

12. The process which comprises heating to boiling a mixture of maleic anhydride, naphthalene and carbon disulfide in the presence of aluminum chloride and fusing the intermediate product thus obtainable with sodium aluminum chloride at a temperature of about '120 to 140 C.

' 13. As a new product, a compound showin the characteristics of cyclic ketones being so uble in concentrated sulfuric acid to a yellow solution with an intense moss-green fluorescence and being obtainable by causing maleic anhydride to act upon an aromatic hydrocarbon having an unsubstituted periposition in the presence of an acid condensing agent.

14. As a new product, a compound showing the characteristics of cyclic ketones being soluble in concentrated sulfuric acid to a yellow solution with an intense moss-green .fluorescence and being obtainable by causin maleic anhydride to act upon acompound o the general formula:

wherein X stands for hydrogen or a monovalent substituent and the two Ys stand for hydrogen atoms or jointly for the group E L- H2 in the presence of an acid condensing agent.

15. As a new compound, the condensation product of maleic anhydride with naphtha- .lene which, when recrystallized from diluted alcohol, forms colorless leaflets melting at 186 C. to 187 C. being soluble in strong sul: furic acid to a faintly yellow solution with an intense moss-green fluorescence and showing the characteristic of cyclic ketones.

In testimony whereof, I afiix my signature.

HEINRICH GREUNEt 

